Silver Anniversary of the Renaissance in Metallocorrole Chemistry

Chemical Reviews, Год журнала: 2025, Номер unknown

Опубликована: Фев. 12, 2025

The 1999 discovery of one-pot corrole synthesis opened the floodgates for research on these unique macrocyclic chelating agents. enormous impact this has been documented in numerous reviews describing advances synthetic chemistry corroles and selected applications which are key components. Our silver anniversary review focuses structures reactions all well characterized corrole-chelated d- p-block metal complexes, including discussions their electronic excited-state physics chemistry. Emphasis is placed structure trinegative N4 coordination core, stabilizes high-valent metals activates low-valent ones, and, importantly, profoundly influences ground- reactivity. story highlights properties that have made them molecular components choice a plethora applications. These include utility sensing gases anions, rescue vital biomolecules from oxidative damage, destruction cancerous cells, catalysis critical organic synthesis, as those involved clean energy processes such production hydrogen reduction oxygen. In our view, will continue to grow by leaps bounds, most especially areas human health renewable science technology.

Язык: Английский

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Chiral iron porphyrin (+)-D₄-(por)FeCl catalyzes highly enantioselective cyclopropanation of alkenes using in situ generated diazoacetonitrile with up to 35 000 product turnover

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Transition metal-catalyzed asymmetric cyclopropanation of alkenes is an important strategy to construct chiral cyclopropane skeletons pharmaceutical interest, but highly enantioselective and practical carbene transfer reactions based on Earth abundant bio-compatible metals are still a difficult challenge. In this work, we use iron porphyrin (+)-D4-(por)FeCl catalyst in situ generated α-diazoacetonitrile for arylalkene. This reaction applicable wide range arylalkenes (44 examples) with yield up 99%, diastereomeric ratio (dr) 93 : 7, enantiomeric excess (ee) values 98%. Importantly, the 3,4-difluorostyrene (1.40 g, 10.0 mmol) presence 0.002 mol% as catalyst, turnover number enantioselectivity cyclopropyl nitrile product reached 31 000 88% ee, respectively. Using nitriles starting material, downstream functionalization derivatives including carboxylic acids, cyclopropylamines, cyclopropylmethanamines can be produced key intermediates preparation series bioactive or drug-like molecules. addition, Fe(ii)porphyrin-cyanocarbene intermediate [(-)-D4-(por)FeII(:CHCN)], which directly responsible reaction, has been characterized by 1H NMR, HR ESI-MS, UV-vis ATR-FTIR spectroscopy.

Язык: Английский

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Visible Light Induced B–H Bond Insertion Reaction with Diazo Compounds

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(17), С. 12583 - 12590

Опубликована: Авг. 19, 2024

A protocol induced by visible light for the direct insertion of α-carbonyl carbenes into B–H bond amine-borane adducts has been developed under conditions that are free metal and photocatalyst. This approach provides a straightforward route to various organoboron compounds from diazo with moderate good yields. Mechanistic investigations reveal this photoinduced reaction proceeds through concerted carbene bond, generation α-diazo esters may be rate-determining step.

Язык: Английский

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Recent Synthetic Advances on the Use of Diazo Compounds Catalyzed by Metalloporphyrins

Molecules, Год журнала: 2023, Номер 28(18), С. 6683 - 6683

Опубликована: Сен. 18, 2023

Diazo compounds are organic substances that often used as precursors in synthesis like cyclization reactions, olefinations, cyclopropanations, cyclopropenations, rearrangements, and carbene or metallocarbene insertions into C−H, N−H, O−H, S−H, Si−H bonds. Typically, reactions from diazo catalyzed by transition metals with various ligands modulate the capacity selectivity of catalyst. These can modify enhance chemoselectivity substrate, regioselectivity enantioselectivity reflecting these preferences products. Porphyrins have been catalysts several important for also medicinal applications. In chemistry compounds, porphyrins very efficient when complexed low-cost (e.g., Fe Co) and, therefore, recent years, this has subject significant research. This review will summarize advances studies involving field metalloporphyrins (M−Porph, M = Fe, Ru, Os, Co, Rh, Ir) last five years to provide a clear overview possible opportunities future Also, at end review, properties artificial metalloenzymes hemoproteins biocatalysts broad range applications, namely those concerning carbene-transfer be considered.

Язык: Английский

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Anhydrous Carbene Insertion Reactions: A Synthetic Platform for DNA‐Encoded Library

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер unknown

Опубликована: Ноя. 7, 2023

Abstract An operationally simple anhydrous carbene insertion reaction to construct DNA‐encoded libraries (DEL) is reported. The developed employs visible light photolysis of diazo compounds and Reversible Adsorption Solid Support (RASS) strategy. From readily available amines, alcohols, phenols, carboxylic acids, a variety high‐value molecules, including useful unnatural amino ethers, esters, promising clinical drug derivatives, bioactive molecules have been constructed.

Язык: Английский

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Investigating the Nature of the Onium Ylide and Michael Acceptor in a Rhodium(I)-Catalyzed Multicomponent Reaction

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(14), С. 10040 - 10047

Опубликована: Июль 3, 2023

We computationally study the mechanistic pathway for synthetically valuable cascading N-H functionalization followed by C-C bond-forming reaction. The impetus to such multicomponent reactions catalyzed Rh(I) arises from highly fluxional nature of onium ylide involved, which is often not amenable experimental detection. Our results throw light on an interesting paradigm where binding metal plays a crucial role. provides some much-needed insights expand scope these methodologies broader range asymmetric reactions.

Язык: Английский

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Bifunctionality of dirhodium tetracarboxylates in metallaphotocatalysis

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Ноя. 10, 2023

Metallaphotocatalysis has been recognized as a pivotal catalysis enabling new reactivities. Traditional metallaphotocatalysis often requires two or more separate catalysts and exhibits flaw in cost substrate-tolerance, thus representing an await-to-solve issue catalysis. We herein realize with bifunctional dirhodium tetracarboxylate ([Rh2]) alone. The [Rh2] shows photocatalytic activity of promoting singlet oxygen (1O2) oxidation. By harnessing its activity, the catalyzes photochemical cascade reaction (PCR) via combination carbenoid chemistry 1O2 chemistry. PCR is characterized by high atom-efficiency, excellent stereoselectivities, mild conditions, scalable synthesis, pharmaceutically interesting products. DFT calculations-aided mechanistic study rationalizes pathway interprets origin stereoselectivities PCR. products show inhibitory against PTP1B, being promising treatment type II diabetes cancers. Overall, here we merges Rh-carbenoid

Язык: Английский

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Diastereoselective Synthesis of 4-Hydroxy-2-quinolinones via Formal [2 + 4] Cycloaddition Reactions Using α-Diazo Pyrazoleamides as C2 Synthons

Organic Letters, Год журнала: 2024, Номер 26(26), С. 5554 - 5559

Опубликована: Июнь 24, 2024

A rhodium-catalyzed highly stereoselective formal [2 + 4]-cycloaddition reaction of α-diazo pyrazoleamides and 2-aminophenyl ketones that produces 4-hydroxy-2-quinolinones in good yields with excellent diastereoselectivities has been developed. pyrazolium ylide species is generated from used as a C2 synthon for this cycloaddition. This protocol offers an efficient approach to variety featuring sequential quaternary centers.

Язык: Английский

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Formal Insertion of a Metal Carbene Complex into a σ‐Carbon‐Carbon Bond. Gold‐Catalyzed Synthesis of 3H‐Indoles

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(9), С. 1989 - 1995

Опубликована: Март 8, 2024

Abstract We report here a formal insertion of metal carbene complex in single carbon‐carbon bond. This behavior occurs with the participation an α‐imino gold complex, generated from benzofused triazapentalenes or, one‐pot procedure, their 1‐propargyl‐1 H ‐benzotriazole precursors, and gold‐catalytically activated ynamides. As result, 3 ‐indole derivatives were obtained, formation quaternary center. A computational analysis carried out on reaction mechanism indicates that bulkiness ligand plays key role forcing conformation, which includes aromatic interactions, favors approximation carbenic carbon to reactive site. In addition, negative crossover experiment rules cationic arene migration pathway.

Язык: Английский

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Iron(II) Phthalocyanine-Catalyzed Homodimerization and Tandem Diamination of Diazo Compounds with Primary Amines: Access to Construct Substituted 2,3-Diaminosuccinonitriles in One-Pot

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(11), С. 7718 - 7726

Опубликована: Май 24, 2024

We herein first report the homodimerization and tandem diamination of diazo compounds with primary amines catalyzed by iron(II) phthalocyanine (PcFe(II)), which can construct one C-C bond two C-N bonds within 20 min in one-pot. Compared to traditional metal-catalyzed N-H insertion reaction between reagents, developed almost does not generate product, but homodimerization/tandem product. The proposed mechanism studies indicate that play a crucial role homocoupling via dimerization iron(III)-acetonitrile radical generated from diazoacetonitrile PcFe(II) coordinated bis(amines); β-hydride elimination is involved, then, attack toward carbon atoms on formed followed. Moreover, this novel be used effectively prepare substituted 2,3-diaminosuccinonitriles high yields even up >99:1 d.r., encouragingly these products contain both 1,2-diamines succinonitrile motifs, are classes important organic significant applications many yields. This also suitable for gram-scale preparation 2,3-bis(phenylamino)succinonitrile (

Язык: Английский

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